依據35 USC§119(e)，本申請案主張2012年10月16日申請的U.S.Provisional Application Nos.：61/714,306之優先權，其名稱為“金屬化介電膜之方法”，其全部內容於本文中併入參考。In accordance with 35 USC § 119 (e), the present application claims priority to US Provisional Application Nos.: 61/714,306, filed on Oct. 16, 2012, entitled, Reference is incorporated herein by reference.
本發明大致上關於一種金屬化介電膜，更具體地，及關於一種金屬化電活性聚合物之方法。This invention relates generally to a metalized dielectric film, and more particularly to a method of metalizing an electroactive polymer.
現今使用的很多種裝置依賴於各式各樣的致動器(actuator)以將電能轉換為機械能，相反地，許多發電應用系統(power generation applications)藉將機械作用轉換成電能來操作，以這方式用於得到機械能，相同類型的裝置可意指為一發電器(generator)，同樣地，當使用該構造將物理性激發(諸如振動或壓力)轉換成用於檢測目的之電信號時，可特徵化為一感測器，尚且，該術語“轉換器”可用於統稱地指任何裝置。Many devices used today rely on a wide variety of actuators to convert electrical energy into mechanical energy. Conversely, many power generation applications operate by converting mechanical action into electrical energy to This method is used to obtain mechanical energy, and the same type of device can be referred to as a generator, and similarly, when the configuration is used to convert physical excitation (such as vibration or pressure) into an electrical signal for detection purposes. It can be characterized as a sensor, and the term "converter" can be used to refer collectively to any device.
對轉換器之製造，許多設計考慮因素有利於先進的介電彈性體材料(亦意指為“電活性聚合物”)之選擇及利用，這些考慮因素包括位勢力(potential force)、功率密度、電力轉換(power conversion)/消耗(consumption)、尺寸、重量、成本、回應時間(response time)、工作週期(duty cycle)、服務需求(service requirement)、環境影響(environmental impact)等，是以，於很多應用中，電活性聚合物技術提供一壓電、形狀-記憶合金(shape-memory alloy)及電磁裝置(諸如電動機(motor)及電磁圈(solenoid))之理想取代。For the manufacture of converters, many design considerations favor the selection and utilization of advanced dielectric elastomer materials (also referred to as "electroactive polymers"), including potential forces, power densities, Power conversion/consumption, size, weight, cost, response time, duty cycle, service requirement, environmental impact, etc. In many applications, electroactive polymer technology provides an ideal replacement for a piezoelectric, shape-memory alloy and electromagnetic devices such as motors and solenoids.
一電活性聚合物轉換器包含二個電極，其具有可變形特性及以薄彈性介電材料分開，當將電壓差施於該電極時，帶相反電荷的電極藉由壓縮其間的聚合物介電層而彼此吸引，由於該電極被拉近在一起，當它在平面方向擴展(沿著X-及Y-軸)時，即，膜的位移(displacement)在平面內(in-plane)，該介電聚合物膜變得更薄(Z-軸組成收縮)，該電活性聚合物膜還可經配置用以在與膜結構正交的方向(沿著Z-軸)，即，該膜的位移在平面外，產生移動，例如，U.S.Pat.No.7,567,681揭示電活性聚合物膜構造，其提供平面外位移-亦意指為表面變形或厚度模式偏移。An electroactive polymer converter comprising two electrodes having deformable properties and separated by a thin elastomeric dielectric material, the oppositely charged electrode being dielectrically compressed by compression when a voltage difference is applied to the electrode The layers are attracted to each other, since the electrodes are brought together, when it expands in the planar direction (along the X- and Y-axis), ie, the displacement of the film is in-plane, The dielectric polymer film becomes thinner (Z-axis composition shrinkage), and the electroactive polymer film alsoThe electroactive polymer film construction can be disclosed in a direction orthogonal to the membrane structure (along the Z-axis), i.e., the displacement of the membrane is out of plane, for example, US Pat. No. 7,567,681. It provides out-of-plane displacement - also means surface deformation or thickness mode offset.
該電活性聚合物膜的材料及物理性質可經改變及控制以定制由轉換器經歷的變形，更具體地，當處於活性模式時，諸如該聚合物膜與電極材料之間的相對彈性、該聚合物膜與電極材料之間的相對厚度及/或該聚合物膜及/或電極材料之變化厚度、該聚合物膜及/或電極材料(欲提供局部的活性及非活性區域)之物理圖案、置於該電活性聚合物膜整體上的拉力或預-應變、及對膜上所施予電壓量或誘導的電容之因素可經控制及改變以定制該膜的特性。The material and physical properties of the electroactive polymer film can be altered and controlled to tailor the deformation experienced by the converter, and more particularly, when in an active mode, such as the relative elasticity between the polymer film and the electrode material, The relative thickness between the polymer film and the electrode material and/or the varying thickness of the polymer film and/or electrode material, the physical pattern of the polymer film and/or electrode material (to provide local active and inactive areas) The tensile or pre-strain placed on the electroactive polymer film as a whole, and the amount of voltage applied to the film or the induced capacitance can be controlled and varied to tailor the properties of the film.
眾多的應用存在來自此類電活性聚合物膜產生的優點之效益，不論是否是單獨使用膜或是於一電活性聚合物致動器使用它，許多應用之一者涵括在使用者介面(interface)裝置中使用電活性聚合物轉換器作為致動器以產生觸感的(haptic)、觸覺的(tactile)、振動的反饋(vibrational feedback)(透過施於使用者的身體之力(force)，將資訊傳達(communication)至使用者)等等，有多種使用此類回饋之已知的使用者介面裝置，基本上回應由使用者起始的力，可使用此類回饋之使用者介面裝置的實例包括鍵盤、鍵板(keypad)、遊戲遙控器(game controller)、遠距遙控(remote control)、觸控螢幕(touch screen)、電腦滑鼠(computer mice)、軌跡球(trackball)、觸控筆(stylus stick)、操縱桿(joystick)等。Numerous applications have the benefit of the advantages derived from such electroactive polymer membranes, whether used alone or in an electroactive polymer actuator, one of many applications being included in the user interface ( An electroactive polymer converter is used as an actuator in the device to generate haptic, tactile, and vibrational feedback (through force applied to the user's body) , to communicate information to the user, etc., there are a variety of known user interface devices that use such feedback, basically responding to the force initiated by the user, and the user interface device using such feedback can be used. Examples include a keyboard, a keypad, a game controller, a remote control, a touch screen, a computer mouse, a trackball, and a touch. A stylus stick, a joystick, and the like.
用於消費性電子媒體裝置以及眾多的其它商業性及消費性應用重要部分之電活性聚合物材料，需要提高生產量同時維持膜的精確性及一致性。Electroactive polymer materials used in consumer electronic media devices and in a number of other commercial and consumer applications require increased throughput while maintaining film accuracy and consistency.
許多聚合物膜應用需要高導電度電極，需要可延伸的及/或可撓的電極之裝置諸如電活性聚合物轉換器、薄膜感測器、電容器、及薄膜電池，對要求可撓性及/或伸展性之應用而言，當薄到足以為可撓性時，可能很難使用剛性且會龜裂的金屬性電極，它們特別難以用於諸如可能需要延伸超出可用於金屬薄膜之伸長度達數個百分比或以上的電活性聚合物裝置之應用。Many polymer film applications require high conductivity electrodes, devices that require extendable and/or flexible electrodes such as electroactive polymer converters, thin film sensors, capacitors, and thin film batteries, which require flexibility and/or Or for applications of stretchability, when thin enough to be flexible, it may be difficult to use rigid and cracking metallic electrodes that are particularly difficult to use, such as may need to extend beyond the available elongation of the metal film. Application of several percentages or more of electroactive polymer devices.
以碳為基底的油墨對要求高導電性電極之裝置會過於阻抗，該裝置諸如大區域電活性聚合物(EAP)致動器或發電器。已提出用於這應用之波紋狀(corrugated)電極，諸如敘述於Pei et al.提出之U.S.Pat.No.7,199,501，其揭示使用紋理的或波紋狀金屬性電極以組合電活性聚合物裝置所需的金屬性導電度與伸展性，Pei et al.揭示一種產生這結構之方法，係藉在一預-延伸的膜上沉積一剛性導電性或非-導電性塗層及接著將它鬆弛，以形成波紋。Carbon-based inks are too resistant to devices that require highly conductive electrodesThe device is such as a large area electroactive polymer (EAP) actuator or generator. A corrugated electrode for this application has been proposed, such as that described in US Pat. No. 7,199,501 to Pei et al., which discloses the use of textured or corrugated metallic electrodes to combine electroactive polymer devices. Metallic conductivity and extensibility, Pei et al. disclose a method of producing this structure by depositing a rigid conductive or non-conductive coating on a pre-stretched film and then relaxing it to Form ripples.
於U.S.Pat.No.7,518,284，Benslimane et al.揭示一種方法，其中一聚合物膜被澆注(cast)到一具有波紋狀表面之離形內襯(release liner)內，從該離形內襯中移除該聚合物膜及將金屬膜沉積至該聚合物膜的波紋狀表面上。A method is disclosed in US Pat. No. 7,518,284, Benslimane et al., in which a polymer film is cast into a release liner having a corrugated surface from which the liner is placed. The polymer film is removed and a metal film is deposited onto the corrugated surface of the polymer film.
以Biggs et al.之名申請的WO/2013/049485，揭示一種方法，其中一聚合物膜只部分地經固化的及接著經熱壓紋以圖案化該具紋理(texture)的曝露表面，然後將一金屬膜沉積至該聚合物膜的紋理表面上。WO/2013/049485, filed in the name of Biggs et al., discloses a method in which a polymer film is only partially cured and then heat embossed to pattern the textured exposed surface, and then A metal film is deposited onto the textured surface of the polymer film.
很難將金屬膜沉積至該彈性聚合物的表面上，該彈性聚合物諸如矽酮及聚胺甲酸酯聚合物，其在加工期間會釋氣(outgas)及延伸，在聚合物膜上產生紋理及接著將金屬性膜沉積至該聚合物膜的紋理表面上也是複雜的(及因此高價)。It is difficult to deposit a metal film onto the surface of the elastomeric polymer, such as an anthrone and a polyurethane polymer, which will outgas and extend during processing to produce on the polymer film. The texture and subsequent deposition of the metallic film onto the textured surface of the polymeric film is also complex (and therefore expensive).
直接壓紋技術會需要高的壓力及溫度，特別是用於交聯的膜，通量(throughput)會受到該鍵重排(bond rearrangement)及再-形成的動力學限制，這些方法亦需要分開的金屬化及層壓步驟。Direct embossing techniques require high pressures and temperatures, especially for cross-linked membranes. The throughput is limited by the bond rearrangement and re-forming kinetics. These methods also need to be separated. Metallization and lamination steps.
Pageaud et al.提出的U.S.Pat.No.5,291,642教示一種在金屬化可撓的塑膠膜輥上製造至少一非-金屬化條(strip)之方法及一種使用該等輥製造堆疊的(stacked)或捲繞的電容器之方法，該製造至少一非-金屬化條之方法的一個特性為所述的非-金屬化條係以入射角α的非-零度角度(non-zero angle)在輥的側面施予雷射光束而製得的。A method of making at least one non-metallized strip on a metallized flexible plastic film roll and a stacked or used roll using the rolls are taught by US Pat. No. 5,291,642. A method of winding a capacitor, one characteristic of the method of producing at least one non-metallized strip is that the non-metallized strip is at a side of the roll at a non-zero angle of incidence angle α Made by applying a laser beam.
Okuno et al.於U.S.Pat.No.5,905,628揭示一種金屬化膜電容器，其藉層壓或捲繞一在一面或兩面上具金屬蒸鍍的電極之金屬膜而形成的，使得一對金屬蒸鍍的電極彼此對向，其中在電容器的兩端提供電極引出(lead-out)部分，各金屬蒸鍍的電極係由一鄰接在該電極引出部分的低電阻區域與一比該低電阻區域具有較高電阻的剩餘高電阻區域所構成，一具形成於長度方向(longitudinal direction)與寬度方向(width direction)之複數個細塊(minute block)及在相鄰的細塊間的融合區域之分割電極(split electrode)圖案係形成於該金屬蒸鍍的電極之至少一者上，及電極分隔線(partitioning line)係在該膜的長度方向以固定間隔(regular interval)形成的，該金屬化膜的製作係透過一藉網目加工所形成的具任何圖案之轉動篩圓筒(rotary screen cylinder)由沉積一物質(諸如用於防止金屬沉積於塑膠膜的蒸鍍面上的油)及其後立即沉積蒸鍍的金屬，藉此形成一分割的融合圖案，其在高速蒸鍍期間供作為一保障機制(safeguard mechanism)。A metallized film capacitor is formed by laminating or winding a metal film having metal-deposited electrodes on one or both sides, such that a pair of metal evaporations is provided by U.S. Patent No. 5,905,628. The electrodes are opposite to each other, wherein an electrode lead-out portion is provided at both ends of the capacitor, and each of the metal-deposited electrodes is formed by a low resistance region adjacent to the electrode lead portion and a lower resistance region than a high-resistance residual high-resistance regionA plurality of minute blocks formed in a longitudinal direction and a width direction and a split electrode pattern formed in a fusion region between adjacent thin blocks are formed on the metal evaporation layer At least one of the electrodes and the electrode partitioning line are formed at a regular interval in the longitudinal direction of the film, and the metallized film is formed by any processing formed by mesh processing. The rotary screen cylinder of the pattern is formed by depositing a substance such as an oil for preventing metal deposition on the vapor deposition surface of the plastic film, and immediately depositing the evaporated metal, thereby forming a split fusion. A pattern that serves as a safety mechanism during high speed evaporation.
Okuno et al.提出的U.S.Pat.No.5,942,283提供一種形成於一對金屬化膜上之金屬化膜電容器，各個金屬化膜包括一具形成於上之金屬蒸鍍的電極之介電膜，一個電極具有縱向電極分隔線及由融合區域分開的複數個小塊，同時另一個電極則無，各金屬化膜在整個具有開口形成其中之側壁的篩圓筒上藉移動該膜而形成，相鄰於該側壁，在該篩圓筒內部配置一噴嘴，同時轉動該篩圓筒將該油從該噴嘴噴出，該油通過該側壁及被沉積在該膜上以於其上形成一圖案，隨後，蒸鍍的金屬被沉積在該膜上。A metallized film capacitor formed on a pair of metallized films, each metallized film comprising a dielectric film formed on the metal-deposited electrode, one of which is provided by U.S. Patent No. 5,942,283. The electrode has a longitudinal electrode separation line and a plurality of small pieces separated by the fusion region, while the other electrode is absent, and each metallized film is formed by moving the film on the screen cylinder having the side wall formed with the opening therebetween, adjacent to Disposing a nozzle inside the screen cylinder, and rotating the screen cylinder to eject the oil from the nozzle, the oil passing through the sidewall and being deposited on the film to form a pattern thereon, and then, An evaporated metal is deposited on the film.
Cahalen et al.於U.S.Pat.No.7,190,016中揭示一種結構，其包括一配置在該適用於形成電容器之電極表面上的電容器介電材料，Cahalen et al亦揭示一種形成此種結構之方法。A structure comprising a capacitor dielectric material disposed on the surface of the electrode suitable for forming a capacitor is disclosed by Cahalen et al., U.S. Pat. No. 7,190,016, and a method of forming such a structure is also disclosed by Cahalen et al.
Cox提出的U.S.Pat.No.7,495,887提供一種聚合性介電組成物，其具有一具介電常數介於50至150之順電性(paraelectric)填料，此類組成物據悉相當適合於電子電路(諸如多層印刷電路)、可撓的電路、半導體封裝的及隱藏的膜電容器。U.S. Patent No. 7,495,887, the entire disclosure of which is incorporated herein by reference to U.S. Pat. Such as multilayer printed circuits), flexible circuits, semiconductor packaged and hidden film capacitors.
Rzeznik於U.S.公開專利申請案No.2006/0022304中揭示一種介電結構，其據悉特別適用於提供正型形貌的(positive topography)之具有一層介電材料的電容器，該介電材料包括一摻雜劑(dopant)，亦揭示一種形成此種介電結構之方法，此種介電結構據悉在隨後施用的導電層上顯示高的黏性。A dielectric structure is disclosed in U.S. Patent Application Serial No. 2006/0022304, which is hereby incorporated herein by reference in its entirety in its entirety in its entirety in the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire disclosure Dopants also disclose a method of forming such a dielectric structure which is said to exhibit high viscosity on a subsequently applied conductive layer.
於此項技術領域中仍持續需要一種製造適用於可延伸的薄膜聚合物裝置之高導電性電極之新穎方法，該等電極應選擇地經圖案化或經紋理化。There remains a continuing need in the art for a novel method of making highly conductive electrodes suitable for use in an extensible thin film polymer device that is selectively patterned or textured.
因此，本發明提供一種製造金屬化聚合物-電極複合體(composite)之方法，其包含將一導電性金屬箔從一金屬轉移膜轉移至一聚合物膜的表面，本發明方法可用於製造一在一面或兩面上具有選擇性紋理的、導電性金屬電極之聚合物膜，本發明之方法發現可運用在製造電活性聚合物轉換器及其它要求可撓性或伸展性之薄膜裝置，諸如薄膜電池、感測器、擴音器、反射式塑性顯示器、太陽能電池、及超級電容器。Accordingly, the present invention provides a method of making a metallized polymer-electrode composite comprising transferring a conductive metal foil from a metal transfer film to a surface of a polymer film, the method of the present invention can be used to fabricate a A polymeric film having a selectively textured, electrically conductive metal electrode on one or both sides, the method of the present invention has been found to be useful in the manufacture of electroactive polymer converters and other thin film devices requiring flexibility or extensibility, such as films Batteries, sensors, loudspeakers, reflective plastic displays, solar cells, and supercapacitors.
本發明之該等及其它優點與效益將由以下本文之發明詳細說明顯現。These and other advantages and benefits of the present invention will appear from the detailed description of the invention herein below.
10‧‧‧冷箔堆疊體10‧‧‧Cold foil stack
12‧‧‧基層12‧‧‧ grassroots
14‧‧‧釋離層14‧‧‧ release layer
16‧‧‧底材層16‧‧‧Substrate layer
18‧‧‧導電性金屬層18‧‧‧ Conductive metal layer
19‧‧‧第二底材層19‧‧‧Second substrate layer
20‧‧‧熱印記箔20‧‧‧Hot stamp foil
22‧‧‧載體膜22‧‧‧ carrier film
24‧‧‧釋離層24‧‧‧ release layer
26‧‧‧保護層26‧‧‧Protective layer
28‧‧‧金屬化層28‧‧‧metallization
29‧‧‧上膠層29‧‧‧Glue layer
30‧‧‧熱印記箔30‧‧‧Hot stamp foil
32‧‧‧載體層32‧‧‧ Carrier layer
33‧‧‧第一釋離層33‧‧‧First release layer
34‧‧‧第二釋離層34‧‧‧Second release layer
35‧‧‧保護層3635‧‧‧Protective layer 36
36‧‧‧金屬化層36‧‧‧metallization
38‧‧‧上膠層38‧‧‧Glue layer
為闡明之目的而非限制，現將結合圖式說明本發明，其中：圖1為一冷箔堆疊體之塊狀圖；圖2A為敘述該具有一層釋離層(release layer)之熱印記箔堆疊體(hot stamp foil stack)層組合體(layer composition)的塊狀圖；及圖2B為顯示該具有二層釋離層之熱印記箔堆疊體之層組合體的塊狀圖.The invention will now be described in conjunction with the drawings, in which: FIG. 1 is a block diagram of a cold foil stack; FIG. 2A is a diagram of the hot stamp foil having a release layer. A block diagram of a layer composition of a hot stamp foil stack; and FIG. 2B is a block diagram showing a layer assembly of the hot stamp foil stack having a two-layer release layer.
為闡明之目的而非限制，現將說明本發明。The invention will now be described for purposes of illustration and not limitation.
電活性聚合物裝置及它們的應用之實例敘述於，例如，U.S.Pat.Nos.6,343,129；6,376,971；6,543,110；6,545,384；6,583,533；6,586,859；6,628,040；6,664,718；6,707,236；6,768,246；6,781,284；6,806,621；6,809,462；6,812,624；6,876,135；6,882,086；6,891,317；6,911,764；6,940,221；7,034,432；7,049,732；7,052,594；7,062,055；7,064,472；7,166,953；7,199,501；7,199,501；7,211,937；7,224,106；7,233,097；7,259,503；7,320,457；7,362,032；7,368,862；7,378,783；7,394,282；7,436,099；7,492,076；7,521,840；7,521,847；7,567,681；7,595,580；7,608,989；7,626,319；7,750,532；7,761,981；7,911,761；7,915,789；7,952,261；8,183,739；8,222,799；8,248,750；及於U.S.專利申請公開Nos.：2007/0200457；2007/0230222；2011/0128239；及2012/0126959，其全部於本文中併入參考。Examples of electroactive polymer devices and their use are described, for example, in US Pat. Nos. 6,343,129; 6,376,971; 6,543,110; 6,545,384; 6,583,533; 6,586,859; 6,628,040; 6,664,718; 6,707,236; 6,768,246; 6,781,284; 6,806,621; 6,809,462; 6,812,624; 6,876,135 ; 6,882,086; 6,891,317; 6,911,764; 6,940,221; 7,034,432; 7,049,732; 7,052,594; 7,062,055; 7,064,472; 7,166,953; 7,199,501; 7,199,501; 7,211,937; 7,224,106; 7,233,097; 7,259,503; 7,320,457; 7,362,032; 7,368,862; 7,378,783; 7,394,282; 7,436,099; 7,492,076; 7,521,840; 7,521,847 ; 7, 567, 681; 7, 595, 580; 7, 608, 989; 7, 626, 319; 7, 750, 532; 7, 761, 981; 7, 911, 761; 7, 915, 789; 7, 952, 261; 8, 183, 739; 8, 222, 799; 8, 248, 750; and US Patent Application Publication No.: 2007/0200457; 2007/0230222; 2011/0128239; and 2012/0126959 , all of which are incorporated herein by reference.
本發明之發明人已研發一種使用商業上可取得的金屬箔技術以將一導電性金屬膜轉移至該介電層上之方法，其可在一批次基台(batch basis)上完成，而特別是用於輥-對-輥加工。The inventors of the present invention have developed a technique for using commercially available metal foils.A method of transferring a conductive metal film onto the dielectric layer, which can be done on a batch basis, and in particular for roll-to-roll processing.
金屬轉移箔普遍用於印刷產業，此類箔一般具有多層的基材、釋離層、底材(primer)、及敷金屬(metallization)，此類箔的實例描述於圖1、2A及2B，該等箔可提供有壓紋的全像圖(hologram)及其它紋理，由於該箔一般很薄及以大輥供應，故一熱塑性塑膠(如聚對苯二甲酸乙二酯)基材可在高速度下被壓有波紋及其它紋理，同樣地，該釋離層及底材可使用標準塗布技術(諸如Meyer棒或蒸發塗布)以很高速度濕式-或乾式塗布，該等層體可為很薄，由於一般所用的基材(聚酯類)具有高密度及釋氣相當少(當與多數的塑膠膜相比下)，亦可以高速度進行敷金屬，整個方法較佳可為輥-對-輥方法。Metal transfer foils are commonly used in the printing industry. Such foils typically have multiple layers of substrates, release layers, primers, and metallization. Examples of such foils are depicted in Figures 1, 2A and 2B. The foils can be provided with embossed holograms and other textures. Since the foils are generally thin and supplied by large rolls, a thermoplastic (eg polyethylene terephthalate) substrate can be Corrugated and other textures are pressed at high speeds. Similarly, the release layer and substrate can be wet- or dry coated at a very high speed using standard coating techniques such as Meyer rods or evaporative coating. It is very thin, because the substrate (polyester) generally used has a high density and relatively low outgassing (when compared with most plastic films), it can also be applied at a high speed, and the whole method is preferably a roll. - Pair-roll method.
冷箔經常用於在印刷媒體上產生金屬特性，於本文所述的本發明方法中，較佳可以所希望的圖案將一黏著劑印刷於介電膜上或冷箔上及接著將該冷箔層壓至該介電膜上，當該冷箔基材從該層壓的堆疊體中被移除時，將一薄金屬層轉移至該於黏著劑之圖案中的介電膜，以產生一介電-電極複合體，為產生一可撓的電容器或電活性聚合物裝置，可將另一冷箔施塗於該介電膜的對向表面或兩個介電-電極複合體可被層壓一起。Cold foils are often used to create metallic properties on a printing medium. In the method of the invention described herein, it is preferred to print an adhesive onto a dielectric film or cold foil in a desired pattern and then to apply the cold foil. Laminated to the dielectric film, when the cold foil substrate is removed from the laminated stack, a thin metal layer is transferred to the dielectric film in the pattern of the adhesive to produce a a dielectric-electrode assembly for applying a flexible capacitor or electroactive polymer device, another cold foil can be applied to the opposite surface of the dielectric film or two dielectric-electrode composites can be layered Press together.
於圖1A以塊狀圖顯示冷箔堆疊體10，參照圖1可理解的是，一熱塑性塑膠(如聚對苯二甲酸乙二酯)基層(base layer)12具有一置於其上的釋離層14，該釋離層具有一置於其上的底材層(primer layer)16及一相鄰於該底材層之導電性金屬層18，適合於該金屬層之導電性金屬包括(但非限制於)銀、銅、金、鋁、鋅、鎳、黃銅、錫、青銅、鐵及鉑，以銀、鋁及錫特別適合於本發明，該金屬層18疊置(overlaid)有一第二底材層19。The cold foil stack10 is shown in block diagram in Figure 1A. It will be understood with reference to Figure 1 that a thermoplastic (e.g., polyethylene terephthalate) base layer12 has a release thereon. The release layer14 has a primer layer16 disposed thereon and a conductive metal layer18 adjacent to the substrate layer, and the conductive metal suitable for the metal layer includes However, it is not limited to silver, copper, gold, aluminum, zinc, nickel, brass, tin, bronze, iron, and platinum. Silver, aluminum, and tin are particularly suitable for the present invention. The metal layer18 is overlaid. Second substrate layer19 .
印刷在該冷箔上的特性可具有較高的解析度及較好的尺寸大小控制性，此乃因在一般為軟質彈性體的介電膜之金屬轉移箔基材整體上該金屬轉移箔基材之較高的機械穩定度之故，較佳具有楊氏模量(Young’s modulus)為低於100MPa，該冷箔機械穩定度亦可使其印刷速度比在該軟質介電膜上得到的印刷速度快很多。The characteristics printed on the cold foil can have higher resolution and better dimensional control, because the metal transfer foil base is entirely on the metal transfer foil substrate of a dielectric film which is generally a soft elastomer. Preferably, the Young's modulus is less than 100 MPa, and the mechanical stability of the cold foil can also make the printing speed higher than that obtained on the soft dielectric film. It's much faster.
熱印記箔類似於冷箔及亦可以類似方式被用於本發明方法，但該轉移程序會需要額外的熱及壓力處理以活化該黏著劑層，亦可使用由其它材料製作的具相似堆疊體結構之金屬轉移箔，亦可消去底材層或包括黏著劑層，該底材及/或黏著劑層在使用前亦可經圖案化，該黏著劑可為B-階段的、熱熔的或壓敏性，使用欲改善性能之更相容的或導電性材料(諸如銀)亦是有利的，該紋理亦可經變化以最適化該複合體結構的伸展性同時保持導電度。Hot stamp foils are similar to cold foils and can be used in the process of the invention in a similar manner, but the transfer procedure may require additional heat and pressure treatment to activate the adhesive layer, orThe metal transfer foil having a similar stack structure made of other materials may also eliminate the substrate layer or include an adhesive layer, and the substrate and/or the adhesive layer may also be patterned before use. The adhesive may be For B-stage, hot melt or pressure sensitive, it may also be advantageous to use a more compatible or electrically conductive material (such as silver) to improve performance, the texture may also be varied to optimize the structure of the composite. Extensibility while maintaining electrical conductivity.
於圖2A及2B中以塊狀圖敘述熱印記箔，圖2A提供一具有一層在載體膜22上的釋離層24之熱印記箔20的實例，該釋離層具有一著色及保護層26，在其上具有一相鄰於該保護層26設置的一金屬化層28，該金屬化層覆蓋有一上膠層(sizing layer)29。The hot stamp foil is illustrated in block diagrams in Figures 2A and 2B. Figure 2A provides an example of a thermal imprint foil20 having a release layer24 on a carrier film22 having a pigmented and protective layer26 There is a metallization layer28 disposed adjacent to the protective layer26 , the metallization layer being covered with a sizing layer29 .
圖2B提供一具有在一載體層32上的一第一釋離層33及一第二釋離層34之熱印記箔30的塊狀圖，該第二釋離層34以一著色及保護層35與該金屬化層36分開，金屬化層36可具有一覆蓋它的上膠層38，該金屬化層36亦可在它與上膠層38之間具有一選擇的防蝕層(corrosion protection layer)(圖中未顯示)。2B provides a block diagram of a thermal imprinting foil30 having a first release layer33 and a second release layer34 on a carrier layer32 , the second release layer34 being a colored and protective layer35 separated from the metal layer36, metal layer36 may have a subbing layer on its cover38, the metal layer36 may also be corrosion-proof layer (corrosion protection layer between it and the upper adhesive layer38 having a selected ) (not shown).
本發明方法亦可具有瑕疵-容許度(fault-tolerance)之優點，於此該薄金屬電極能夠消除掉導致局部加熱或介電失效之週遭的瑕疵及缺陷，如此項技術領域所知的，此可斷開電性連接至該瑕疵區域，以電性上隔離該缺陷及使能連續操作。The method of the present invention may also have the advantage of fault-tolerance, whereby the thin metal electrode is capable of eliminating defects and defects that cause localized heating or dielectric failure, as is known in the art. The electrical connection to the crucible region can be broken to electrically isolate the defect and enable continuous operation.
於本發明方法之一具體實施，一介電膜可直接經澆注或經塗布至冷箔的金屬化面上以金屬化該介電膜的底面，本發明之方法在該介電膜已經固化或乾燥之後可另外包含層壓上一插層材料(interleaf material)，該金屬層係黏附至該介電膜及該兩層可一起從該冷箔基材上被移除，該冷箔可具有一至該底材層之圖案或具有一施塗至製作圖案化電極之圖案化黏著劑，該金屬亦可藉已知的圖案化方法(諸如選擇性蝕刻或光刻法(photolithography))被移除，兩層的金屬化介電膜可以濕式或乾式層壓一起以製造一電活性聚合物裝置，在該等層體之間可層壓一介電或導電性黏著劑或分隔層(separate layer)，以製作一多-層堆疊體。In one embodiment of the method of the present invention, a dielectric film can be directly cast or coated onto the metallized surface of the cold foil to metallize the bottom surface of the dielectric film, and the method of the present invention has been cured or After drying, an interleaf material may be additionally laminated, the metal layer is adhered to the dielectric film, and the two layers may be removed together from the cold foil substrate, and the cold foil may have a The pattern of the substrate layer or having a patterned adhesive applied to the patterned electrode, the metal may also be removed by known patterning methods such as selective etching or photolithography. The two-layer metallized dielectric film can be wet or dry laminated together to produce an electroactive polymer device, between which a dielectric or conductive adhesive or separate layer can be laminated. To make a multi-layer stack.
或者是，本發明之方法可用於澆注/塗布該介電膜至一標準離形內襯上，如通常的固化/乾燥，及層壓該冷箔至該膜的上表面(top surface)上，該介電膜較佳具有如一壓敏性黏著劑般的高黏性以幫助從該冷箔基材將金屬層轉移至該介電膜，或者是，在層壓前，可使用一適當的方法施塗一黏著劑以印刷該黏著劑，其還將可使該移轉的金屬圖案化。Alternatively, the method of the present invention can be used to cast/coat the dielectric film onto a standard release liner, such as conventional curing/drying, and laminating the cold foil onto the top surface of the film, The dielectric film preferably has a high viscosity like a pressure sensitive adhesive to assist from the cold foil substrateThe metal layer is transferred to the dielectric film, or, prior to lamination, an adhesive can be applied using an appropriate method to print the adhesive, which will also pattern the transferred metal.
本發明方法可包括上述步驟之組合：在該介電膜已至少部分地經固化/乾燥之後，澆注至該冷箔上及層壓至另一層冷箔，此具體實施之優點為避免使用諸如離形內襯及插層之類的額外耗材(consumables)。The method of the present invention may comprise a combination of the above steps: after the dielectric film has been at least partially cured/dried, cast onto the cold foil and laminated to another layer of cold foil, this embodiment has the advantage of avoiding the use of Additional consumables such as linings and intercalations.
於所有具體例中，可採取保護以避免經由操作使該金屬膜產生龜裂，諸如當移除該冷箔基材時延伸該介電膜或製作通孔(through-hole)(“通道(via)”)連接時，還有，移除該釋離層或在轉移的金屬膜表面上的底材可有助於表面電性連接的使用(可能使用電性上導電性黏著劑)。In all embodiments, protection may be employed to avoid cracking of the metal film via operation, such as extending the dielectric film or making through-holes when the cold foil substrate is removed ("via" When the connection is made, the removal of the release layer or the substrate on the surface of the transferred metal film may contribute to the use of the surface electrical connection (possibly using an electrically conductive adhesive).
雖然本發明方法之意欲的應用係用於電活性聚合物轉換器，本發明之發明人發現它可運用於其它要求可撓性及/或伸展性之薄膜裝置，諸如薄膜電池、感測器、擴音器、反射式塑性顯示器、太陽能電池、及超級電容器。Although the intended application of the method of the present invention is for an electroactive polymer converter, the inventors of the present invention have found that it can be applied to other thin film devices requiring flexibility and/or stretchability, such as thin film batteries, sensors, Loudspeakers, reflective plastic displays, solar cells, and supercapacitors.
本發明進一步(但非受限制)藉由下述實施例說明。The invention is further, but not limited, illustrated by the following examples.
使用一專利的、二-部分、加成(addition)-經固化的矽酮彈性體調配物作為用於電活性聚合物轉換器之介電彈性體，經澆注至一獲自API(Santa Fe Springs,CA,USA)之全像的箔膜；在150℃下，經固化3分鐘。A patented, two-part, addition-cured fluorenone elastomer formulation was used as a dielectric elastomer for an electroactive polymer converter, cast to an API (Santa Fe Springs) , CA, USA) Fully foil film; cured at 150 ° C for 3 minutes.
在固化後，將該介電膜從該箔基材中移除，及將該敷金屬乾淨地移轉至該介電膜的表面；使用剃刀片(razor blade)接觸，以裂過該敷金屬之表面上的釋離層底材，測得約2e-4 siemens的導電率；該金屬化層的表導電度(sheet conductivity)預期會較高；移轉前該膜本身具有一約3e-2 siemens/sq的表面導電度-但在該接觸點的周圍觀察到細微龜裂(microcrack)及據信這些龜裂增加了對測量之明顯互連電阻。After curing, the dielectric film is removed from the foil substrate and the metallization is cleanly transferred to the surface of the dielectric film; contact is made using a razor blade to crack the metallization The release layer substrate on the surface has a conductivity of about 2e-4 siemens; the sheet conductivity of the metallization layer is expected to be higher; the film itself has a thickness of about 3e-2 before transfer. The surface conductivity of siemens/sq - but microcracks were observed around the contact point and it is believed that these cracks increase the apparent interconnect resistance to the measurement.
同樣地，該敷金屬成功地層壓至丙烯酸酯及矽酮壓敏性黏著劑材料二者；一矽酮與矽酮壓敏性黏著劑之雙澆注層亦可行。Similarly, the metallization is successfully laminated to both the acrylate and anthrone pressure sensitive adhesive materials; a double cast layer of an anthrone and an anthrone pressure sensitive adhesive can also be used.
三層樣品製作，係利用一獲自K Laser(Garden Grove,CA,USA)之全像的冷箔膜，依序藉澆注及固化矽酮壓敏性黏著劑、矽酮彈性體、及矽酮壓敏性黏著劑至該箔上，接著藉層壓另一片箔；在移除該離形內襯之後，測得0.05之導電率。The three-layer sample was fabricated by a cold foil film obtained from a holographic image of K Laser (Garden Grove, CA, USA), sequentially casting and curing an anthrone pressure sensitive adhesive, an anthrone elastomer, and an anthrone. Pressure sensitive adhesive onto the foil, followed by lamination of another foil; removal of the release linerThereafter, a conductivity of 0.05 was measured.
本文所述的各方面的標的物，依下述編號條項以其任何組合方式闡述：The subject matter of the various aspects described herein is set forth in any combination of the following numbered items:
1.一種製造金屬化聚合物-電極複合體之方法，包含將一導電性金屬箔從一金屬轉移膜轉移至一聚合物膜的表面。A method of making a metallized polymer-electrode assembly comprising transferring a conductive metal foil from a metal transfer film to a surface of a polymer film.
2.根據請求項1之方法，其中該轉移的步驟包含：澆注一可固化的聚合物膜-形成調配物至一其上具有導電性金屬箔之導電性金屬轉移膜之表面上；固化該調配物，以形成一聚合物膜，其具有一與該其上具有導電性金屬箔之導電性金屬轉移膜接觸的第一表面；及從該轉移金屬箔至該聚合物膜的第一表面之導電性金屬轉移膜上移除該經固化的聚合物膜。2. The method of claim 1, wherein the transferring comprises: casting a curable polymer film - forming a formulation onto a surface of a conductive metal transfer film having a conductive metal foil thereon; curing the blending Forming a polymer film having a first surface in contact with the conductive metal transfer film having the conductive metal foil thereon; and conducting electricity from the transfer metal foil to the first surface of the polymer film The cured polymer film is removed from the metal transfer film.
3.根據請求項1及2之一項之方法，另包含層壓兩種聚合物-電極複合體，以形成一電極-聚合物-電極複合體。3. The method according to one of claims 1 and 2, further comprising laminating two polymer-electrode composites to form an electrode-polymer-electrode composite.
4.根據請求項1及2之一項之方法，另包含配設一第二電極至該聚合物膜的對向面，以形成一電極-聚合物-電極複合體。4. The method of any one of claims 1 and 2, further comprising disposing a second electrode to the opposite side of the polymer film to form an electrode-polymer-electrode composite.
5.根據請求項4之方法，其中該第二電極包含一從一第二導電性金屬轉移膜轉移的第二金屬箔。5. The method of claim 4, wherein the second electrode comprises a second metal foil transferred from a second conductive metal transfer film.
6.根據請求項1至5中任一項之方法，其中重複該澆注、固化及移除之步驟，以形成一多層聚合物電極複合體。6. The method of any one of claims 1 to 5, wherein the step of casting, curing and removing is repeated to form a multilayer polymer electrode composite.
7.根據請求項1至6中任一項之方法，其中該導電性金屬箔具有一紋理或一波紋，其能夠被延伸而不會減損導電度。The method of any one of claims 1 to 6, wherein the conductive metal foil has a texture or a corrugation that can be extended without detracting from electrical conductivity.
8.根據請求項1至7中任一項之方法，其中該導電性金屬轉移膜另包含一圖案化的轉移層。The method of any one of claims 1 to 7, wherein the conductive metal transfer film further comprises a patterned transfer layer.
9.根據請求項8之方法，其中該圖案化的轉移層係選自包括一圖案化的黏著劑及一圖案化的底材層所構成組群。9. The method of claim 8, wherein the patterned transfer layer is selected from the group consisting of a patterned adhesive and a patterned substrate layer.
10.根據請求項1至9中任一項之方法，其中該聚合物係選自包括矽酮、丙烯酸酯及聚胺甲酸酯所構成組群。The method of any one of claims 1 to 9, wherein the polymer is selected from the group consisting of an anthrone, an acrylate, and a polyurethane.
11.根據請求項1至10中任一項之方法，其中該聚合物包含一壓敏性黏著劑。The method of any one of claims 1 to 10, wherein the polymer comprises a pressure sensitive adhesive.
12.根據請求項1至11中任一項之方法，其中該金屬轉移膜係選自包括冷箔及熱印記箔所構成組群。The method of any one of claims 1 to 11, wherein the metal transferThe film system is selected from the group consisting of a cold foil and a hot stamp foil.
13.一種電活性聚合物轉換器，其包括根據請求項1至12中任一項之方法製作的金屬化聚合物-電極複合體。13. An electroactive polymer converter comprising a metalized polymer-electrode composite made according to the method of any one of claims 1 to 12.
前述本發明之實例係提供說明目的而非限制，此項技術領域熟悉者將顯而易見本文所述的具體實施在不偏離本發明之精神及範疇下可以各種方式被修飾或修正，本發明範疇圍由隨附的請求項被評量。The foregoing examples of the present invention are intended to be illustrative and not restrictive, and it will be apparent to those skilled in the art that the invention can be modified or modified in various ways without departing from the spirit and scope of the invention. The attached request item is evaluated.
10‧‧‧冷箔堆疊體10‧‧‧Cold foil stack
12‧‧‧基層12‧‧‧ grassroots
14‧‧‧釋離層14‧‧‧ release layer
16‧‧‧底材層16‧‧‧Substrate layer
18‧‧‧導電性金屬層18‧‧‧ Conductive metal layer
19‧‧‧第二底材層19‧‧‧Second substrate layer
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| US201261714306P | 2012-10-16 | 2012-10-16 |
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| TW102137107ATW201436311A (en) | 2012-10-16 | 2013-10-15 | Method of metallizing dielectric film |
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